BACKGROUND
FIELD
[0001] Aspects of embodiments of the present disclosure relate to a method for manufacturing
a dry electrode film, a dry electrode film, and a dry electrode including the dry
electrode film.
DESCRIPTION OF THE RELATED ART
[0002] Unlike primary batteries that are not designed to be (re)charged, secondary (or rechargeable)
batteries are typically designed to be discharged and recharged. Low-capacity secondary
batteries are typically used in portable, small electronic devices, such as smart
phones, feature phones, notebook computers, digital cameras, and camcorders, while
large-capacity secondary batteries are widely used as power sources for driving motors
in hybrid vehicles and electric vehicles and for storing power (e.g., home and/or
utility scale power storage). A secondary battery generally includes an electrode
assembly including a positive electrode and a negative electrode, a case accommodating
the same, and electrode terminals connected to the electrode assembly.
[0003] A dry electrode may include an electrode substrate, an active material, a binder,
and a conductive material. A film type dry electrode film may be formed by pressurizing
the active material, the binder, and the conductive material. The dry electrode may
be manufactured by joining the electrode substrate and the dry electrode film through
a lamination process. The mechanical stability of the dry electrode film may be an
advantageous factor, and thus various efforts may be made to predict a mechanical
property in advance.
[0004] The above information disclosed in this Background section is for enhancement of
understanding of the background of the present disclosure, and therefore, it may contain
information that does not constitute related (or prior) art.
SUMMARY
[0005] The present disclosure addresses at least the above technical problems, and aspects
of example embodiments of the present disclosure include a method for manufacturing
a dry electrode film, a dry electrode film, and a dry electrode including same.
[0006] These and other aspects and features of the present disclosure are described in,
or are apparent from, the following description of example embodiments of the present
disclosure.
[0007] In order to realize the objective, according to example embodiments of the present
disclosure, a method for manufacturing a dry electrode film includes preparing a dry
mixture by dry mixing an active material, a conductive material, and a binder, manufacturing
a mixture lump by kneading the dry mixture, obtaining an electrode powder by crushing
the mixture lump, manufacturing a specimen using the electrode powder through a mold,
testing a yield strength of the specimen, and manufacturing, when a test result of
the yield strength satisfies a predetermined or desired criterion, a sheet type dry
electrode film having a given thickness by calendaring the electrode powder.
[0008] According to example embodiments, the manufacturing of the specimen using the electrode
powder through the mold may include filling the electrode powder in the mold, and
pressurizing the electrode powder filled in the mold.
[0009] According to example embodiments, the filling of the electrode powder in the mold
may include filling the electrode powder in the mold so that a weight of the electrode
powder filled in the mold is in a range of about 1 g to about 5 g.
[0010] According to example embodiments, the pressurizing of the electrode powder filled
in the mold may include pressurizing the electrode powder at a pressure of in a range
of about 10 MPa to about 100 MPa using a pressurizing member.
[0011] According to example embodiments, the testing of the yield strength of the specimen
may include pressurizing the specimen to be destroyed using a jig, measuring a load
applied to the specimen at a moment when the specimen is destroyed, and calculating
the yield strength of the specimen based on the measured load.
[0012] According to example embodiments, the calculating of the yield strength of the specimen
may include calculating the yield strength of the specimen based on Equation 1 below.

[0013] According to example embodiments, the testing of the yield strength of the specimen
may further include, after the calculating of the yield strength of the specimen,
crushing the electrode powder when the yield strength calculated by Equation 1 is
less than a given value.
[0014] According to example embodiments, the given value may be about 2.3 MPa.
[0015] According to example embodiments, the testing of the yield strength of the specimen
may further include, after the calculating of the yield strength of the specimen,
measuring an angle of internal friction of the electrode powder, and calculating a
tensile strength of the specimen.
[0016] According to example embodiments, the measuring of the angle of internal friction
of the electrode powder may include measuring the angle of internal friction of the
electrode powder using a powder fluidity evaluation method.
[0017] According to example embodiments, the calculating of the tensile strength of the
specimen may include calculating the tensile strength of the specimen based on Equation
2 below.

[0018] According to example embodiments, the calculating of the tensile strength of the
specimen may further include, after the calculating of the tensile strength of the
specimen, crushing the electrode powder when the tensile strength calculated by Equation
2 is less than a given value.
[0019] According to example embodiments, the given value may be equal to about 0.5 MPa.
[0020] According to example embodiments of the present disclosure, a dry electrode film
includes an electrode powder including an active material, a conductive material,
and a binder, wherein the electrode powder has a sheet shape manufactured through
calendaring and has a given thickness, and a yield strength of the electrode powder
is in a range of about 2.3 MPa or more in a sheet shape state.
[0021] According to example embodiments, an angle of internal friction of the electrode
powder may be in a range of about 30° to about 50°.
[0022] According to example embodiments, a tensile strength of the dry electrode film may
be in a range of about 0.5 MPa or more.
[0023] According to example embodiments, a porosity of the dry electrode film may be in
a range of about 50 % to about 70 %.
[0024] According to example embodiments, the active material may include at least one of
nickel cobalt aluminum (NCA), lithium ferrophosphate (LFP), and graphite.
[0025] According to example embodiments, the binder may include at least one of polytetrafluoroethylene
(PTFE), polyvinylidene fluoride (PVDF), and polyacrylonitrile (PAN).
[0026] According to example embodiments of the present disclosure, a dry electrode includes
a substrate, and a dry electrode film on at least one surface of the substrate. The
dry electrode film includes an electrode powder including an active material, a conductive
material, and a binder, and the electrode powder has a sheet shape manufactured through
calendaring and having a given thickness. A yield strength of the electrode powder
is in a range of about 2.3 MPa or more in a sheet shape state.
[0027] According to some example embodiments of the present disclosure, a method for manufacturing
a dry electrode film with an improved mechanical property, a dry electrode film, and
a dry electrode including the same may be disclosed.
[0028] According to some example embodiments of the present disclosure, a method for manufacturing
a dry electrode film with an improved mechanical property by testing a mechanical
property of an electrode powder before the electrode powder is calendared and then
manufactured into the dry electrode film, a dry electrode film, and a dry electrode
including the same may be disclosed.
[0029] According to some example embodiments of the present disclosure, a specimen may be
manufactured with a small amount of electrode powder before the electrode powder is
calendared and then manufactured into a dry electrode film, and thus the mechanical
property may be readily measured.
[0030] However, aspects and features of the present disclosure are not limited to those
described above, and other aspects and features not mentioned are clearly understood
by a person skilled in the art from the detailed description, described below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The following drawings attached to this specification illustrate example embodiments
of the present disclosure, and further describe aspects and features of the present
disclosure together with the detailed description of the present disclosure. Thus,
the present disclosure should not be construed as being limited to the drawings:
FIG. 1 is a flowchart illustrating an example of a method for manufacturing a dry
electrode film, according to some example embodiments of the present disclosure
FIG. 2 is a diagram explaining a method for manufacturing a dry electrode film, according
to some example embodiments of the present disclosure.
FIG. 3 is a diagram illustrating an example of a mold and a pressurizing member, according
to some example embodiments of the present disclosure.
FIG. 4 is a diagram illustrating an example of filling an electrode powder in a mold,
according to some example embodiments of the present disclosure.
FIG. 5 is a diagram illustrating an example of an electrode powder filled in a mold
and a pressurizing member, according to some example embodiments of the present disclosure.
FIG. 6 is a diagram illustrating an example of pressurizing an electrode powder filled
in a mold, according to some example embodiments of the present disclosure.
FIG. 7 is a diagram illustrating an example of a specimen manufactured using an electrode
powder, according to some example embodiments of the present disclosure.
FIG. 8 is a diagram illustrating an example of a specimen pressurized by a jig and
measure equipment which measures a load, according to some example embodiment of the
present disclosure
FIG. 9 is a diagram illustrating Equation 1 for calculating a yield strength of a
specimen based on a measured load, according to some example embodiment of the present
disclosure.
FIG. 10 is a diagram illustrating Equation 2 for calculating a tensile strength of
a specimen based on a measured angle of internal friction (AIF) and a calculated yield
strength of a specimen, according to some example embodiments of the present disclosure.
FIG. 11 illustrates a cross-sectional view of an example of a dry electrode according
to some example embodiments of the present disclosure.
DETAILED DESCRIPTION
[0032] Hereinafter, embodiments of the present disclosure are described, in detail, with
reference to the accompanying drawings. The terms or words used in this specification
and claims should not be construed as being limited to the usual or dictionary meaning
and should be interpreted as meaning and concept consistent with the technical idea
of the present disclosure based on the principle that the inventor can be their own
lexicographer to appropriately define the concept of the term to explain the disclosure
in the best way.
[0033] The example embodiments described in this specification and the configurations shown
in the drawings are only some of the example embodiments of the present disclosure
and do not represent all of the technical spirit, aspects, and features of the present
disclosure. Accordingly, it should be understood that there may be various equivalents
and modifications that can replace or modify the example embodiments described herein
at the time of filing this application.
[0034] It is understood that when an element or layer is referred to as being "on," "connected
to," or "coupled to" another element or layer, it may be directly on, connected, or
coupled to the other element or layer, or one or more intervening elements or layers
may also be present. When an element or layer is referred to as being "directly on,"
"directly connected to," or "directly coupled to" another element or layer, there
are no intervening elements or layers present. For example, when a first element is
described as being "coupled" or "connected" to a second element, the first element
may be directly coupled or connected to the second element, or the first element may
be indirectly coupled or connected to the second element via one or more intervening
elements.
[0035] In the figures, dimensions of the various elements, layers, and the like, may be
exaggerated for clarity of illustration. The same reference numerals designate the
same elements. As used herein, the term "and/or" includes any and all combinations
of one or more of the associated listed items. Further, the use of "may" when describing
example embodiments of the present disclosure relates to "one or more embodiments
of the present disclosure." Expressions, such as "at least one of" and "any one of,"
when preceding a list of elements, modify the entire list of elements and do not modify
the individual elements of the list. When phrases such as "at least one of A, B and
C, "at least one of A, B or C," "at least one selected from a group of A, B and C,"
or "at least one selected from among A, B and C" are used to designate a list of elements
A, B and C, the phrase may refer to any and all suitable combinations or a subset
of A, B and C, such as A, B, C, A and B, A and C, B and C, or A and B and C. As used
herein, the terms "use," "using," and "used" may be considered synonymous with the
terms "utilize," "utilizing," and "utilized," respectively. As used herein, the terms
"substantially," "about," and similar terms are used as terms of approximation and
not as terms of degree, and are intended to account for the inherent variations in
measured or calculated values that would be recognized by those of ordinary skill
in the art.
[0036] It is understood that, although the terms first, second, third, and the like, may
be used herein to describe various elements, components, regions, layers, and/or sections,
these elements, components, regions, layers, and/or sections should not be limited
by these terms. These terms are used to distinguish one element, component, region,
layer, or section from another element, component, region, layer, or section. Thus,
a first element, component, region, layer, or section discussed below could be termed
a second element, component, region, layer, or section without departing from the
teachings of example embodiments.
[0037] Spatially relative terms, such as "beneath," "below," "lower," "above," "upper,"
and the like, may be used herein for ease of description to describe one element or
feature's relationship to another element(s) or feature(s) as illustrated in the figures.
It is understood that the spatially relative terms are intended to encompass different
orientations of the device in use or operation in addition to the orientation depicted
in the figures. For example, if the device in the figures is turned over, elements
described as "below" or "beneath" other elements or features would then be oriented
"above" or "over" the other elements or features. Thus, the term "below" may encompass
both an orientation of above and below. The device may be otherwise oriented (rotated
90 degrees or at other orientations), and the spatially relative descriptors used
herein should be interpreted accordingly.
[0038] The terminology used herein is for the purpose of describing example embodiments
of the present disclosure and is not intended to be limiting the present disclosure.
As used herein, the singular forms "a" and "an" are intended to include the plural
forms as well, unless the context clearly indicates otherwise. It is further understood
that the terms "includes," "including," "comprises," and/or "comprising," when used
in this specification, specify the presence of stated features, integers, steps, operations,
elements, and/or components but do not preclude the presence or addition of one or
more other features, integers, steps, operations, elements, components, and/or groups
thereof.
[0039] Also, any numerical range disclosed and/or recited herein is intended to include
all sub-ranges of the same numerical precision subsumed within the recited range.
For example, a range of "1.0 to 10.0" is intended to include all subranges between
(and including) the recited minimum value of 1.0 and the recited maximum value of
10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value
equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical
limitation recited herein is intended to include all lower numerical limitations subsumed
therein, and any minimum numerical limitation recited in this specification is intended
to include all higher numerical limitations subsumed therein. Accordingly, Applicant
reserves the right to amend this specification, including the claims, to expressly
recite any sub-range subsumed within the ranges expressly recited herein.
[0040] References to two compared elements, features, and the like, as being "the same"
may mean that they are "substantially the same." Thus, the phrase "substantially the
same" may include a case having a deviation that is considered low in the art, for
example, a deviation of 5% or less. In addition, when a given parameter is referred
to as being uniform in a given region, it may mean that it is uniform in terms of
an average.
[0041] Throughout the specification, unless otherwise stated, each element may be singular
or plural.
[0042] Arranging an arbitrary element "above (or below)" or "on (under)" another element
may indicated that the arbitrary element may be disposed in contact with the upper
(or lower) surface of the element, and another element may also be interposed between
the element and the arbitrary element disposed on (or under) the element.
[0043] In addition, it is understood that when a component is referred to as being "linked,"
"coupled," or "connected" to another component, the elements may be directly "coupled,"
"linked" or "connected" to each other, or another component may be "interposed" between
the components".
[0044] Throughout the specification, when "A and/or B" is stated, it means A, B or A and
B, unless otherwise stated. That is, "and/or" includes any or all combinations of
a plurality of items enumerated. When "C to D" is stated, it means C or more and D
or less, unless otherwise specified.
[0045] As discussed above, when the terms "about" or "substantially" are used in this specification
in connection with a numerical value, it is intended that the associated numerical
value include a tolerance of ±10% around the stated numerical value. When ranges are
specified, the range includes all values therebetween such as increments of 0.1%.
[0046] In the present disclosure, dimensions and relative dimensions of layers and regions
illustrated in drawings may be exaggerated for clarity of explanation. That is, the
dimensions illustrated in drawings are only for convenience of understanding and are
not limited thereto. Further, the same reference numerals throughout the specification
designate the same elements.
[0047] FIG. 1 is a flowchart illustrating an example of a method for manufacturing a dry
electrode film, according to some example embodiments of the present disclosure, and
FIG. 2 is a diagram explaining a method for manufacturing a dry electrode film, according
to some example embodiments of the present disclosure. The method for manufacturing
a dry electrode film illustrated in FIG. 2, may include a mixing process 410, a kneading
process 420, a crushing process 430, a specimen manufacturing process 440, a process
450 for testing a yield strength of the specimen, and a calendaring process 460 which
includes passing the material through one or more rollers.
[0048] Referring to FIG. 1, a method S300 for manufacturing a dry electrode film may include
preparing a dry mixture by dry mixing an active material, a conductive material, and
a binder (S310). For example, the dry mixture may be manufactured by dry mixing the
active material, the conductive material, and the binder through the mixing process
410 illustrated in FIG. 2.
[0049] Referring to FIG. 1, a mixture lump may be manufactured by kneading the dry mixture
(S320). For example, the dry mixture may be formed into the mixture lump through the
kneading process 420 illustrated in FIG. 2. In this example, the binder included in
the dry mixture may receive shearing force to be fibrillized in the kneading process
420. The fibrillized binder may allow the active material and the conductive material
included in the dry mixture to be combined or coupled together. For example, the mixture
lump may be formed using a kneader.
[0050] Referring to FIG. 1, a powder for an electrode (hereinafter, referred to as electrode
powder 520 illustrated in FIG. 2) may be obtained by crushing the mixture lump (S330).
For example, the mixture lump may be formed into the electrode powder 520 through
the crushing process 430 illustrated in FIG. 2. In this example, the crushing process
430 may be performed using a crusher. The crushed electrode powder 520 may be formed,
and thus the film formation of the electrode powder 520 may be facilitated.
[0051] Referring to FIG. 1, a specimen may be manufactured using the electrode powder 520
through a mold (S340).
[0052] In some example embodiments, the process S340 for manufacturing a specimen (see 800
of FIG. 7) using the electrode powder 520 through a mold (see 510 of FIG. 3) may include
a process for filling the electrode powder 520 in the mold 510 and a process for pressurizing
the electrode powder 520 filled within the mold 510. In some example embodiments,
the process of filling the electrode powder 520 in the mold 510 may include a process
for filling the electrode powder 520 in the mold 510 so that the weight of the electrode
powder 520 filled within the mold 510 is in a range of about 1 g to about 5 g. In
some example embodiments, the process of pressurizing the electrode powder 520 filled
within the mold 510 may include a process of pressurizing the electrode powder 520
at a pressure in a range of about 10 MPa to about 100 MPa using a pressurizing member
(see 530 of FIG. 3 and FIG. 5).
[0053] Referring back to FIG. 1, a yield strength of the specimen may be tested S350.
[0054] In some example embodiments, the process S350 of testing the yield strength of the
specimen 800 may include a process of pressurizing the specimen 800 to be destroyed
using a jig (see 900 of FIG. 8), a process of measuring a load applied to the specimen
800 at a moment when the specimen 800 is destroyed, and a process of calculating the
yield strength of the specimen 800 based on the measured load.
[0055] In some example embodiments, the process of calculating the yield strength of the
specimen 800 may include a process of calculating the yield strength of the specimen
based on the following Equation 1.

[0056] In some example embodiments, after the process of calculating the yield strength
of the specimen, the method S300 for manufacturing a dry electrode film may further
include a process of crushing the electrode powder 520 when the yield strength calculated
by Equation 1 is less than a given value. In some example embodiments, the given value
may be equal to about 2.3 MPa. Through the crushing process, the binder may be crushed
in a fine fiber form, and thus a surface area of the binder may be increased, the
particles may be finer, and the porosity may be increased. Accordingly, the mechanical
property of the dry electrode film may be improved.
[0057] In some example embodiments, after the process of calculating the yield strength
of the specimen 800, the method S300 for manufacturing a dry electrode film may further
include a process of measuring an angle of internal friction (AIF) of the electrode
powder 520, and a process of calculating a tensile strength of the specimen 800. In
some example embodiments, the process of measuring the angle of internal friction
(AIF) of the electrode powder may include a process of measuring the angle of internal
friction (AIF) of the electrode powder 520 using a powder fluidity evaluation method.
[0058] In some example embodiments, the process of calculating the tensile strength of the
specimen may include a process of calculating the tensile strength of the specimen
based on the following Equation 2.

[0059] In some example embodiments, after the process of calculating the tensile strength
of the specimen 800, the method S300 for manufacturing a dry electrode film may further
include a process of crushing the electrode powder 520 when the tensile strength calculated
by Equation 2 is less than a given value. In some example embodiments, the given value
may be equal to about 0.5 MPa.
[0060] Referring back to FIG. 1, when the test result of the yield strength satisfies a
predetermined or desired criterion, the sheet type dry electrode film having a given
thickness may be manufactured by calendaring the electrode powder (S360). For example,
the crushed electrode powder 520 may be formed into the dry electrode film through
the calendaring process 460. In this example, the calendaring process may allow the
fibrillized binder to combine or couple the active material and the conductive material,
and to support or maintain the film shape so that the dry electrode film may be formed.
In examples, the dry electrode film may be formed without a separate solvent.
[0061] The dry electrode film may be formed in a free-standing film form. For example, the
free-standing film may be referred to as a film which may be formed independently
without being laminated to a substrate. In this example, after the dry electrode film
is formed in the free-standing film form, the dry electrode film may be laminated
to the substrate.
[0062] The dry electrode film may include the active material, the conductive material,
and the binder. For example, the active material may be or include a positive electrode
active material or a negative electrode active material.
[0063] The positive electrode active material may include a compound (lithiated intercalation
compound) that is capable of intercalating and deintercalating lithium. For example,
at least one of a composite oxide of lithium and a metal such as or including at least
one of cobalt, manganese, nickel, and combinations thereof may be included.
[0064] The composite oxide may be or include a lithium transition metal composite oxide.
Specific examples of the composite oxide may include at least one of lithium nickel-based
oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based
compound, cobalt-free nickel-manganese-based oxide, or a combination thereof.
[0065] As an example, the following compounds represented by any one of the following Chemical
Formulas may be included. LiaA1-bXbO2-cDc (0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); LiaMn2-bXbO4-cDc
(0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); LiaNi1-b-cCobXcO2-αDα (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5,
and 0<α<2); LiaNi1-b-cMnbXcO2-αDα (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, and 0<α<2); LiaNibCocL1dGeO2
(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, and 0≤e≤0.1); LiaNiGbO2 (0.90≤a≤1.8 and 0.001≤b≤0.1);
LiaCoGbO2 (0.90≤a≤1.8 and 0.001 ≤b≤0.1); LiaMn1-bGbO2 (0.90≤a≤1.8 and 0.001 ≤b≤0.1);
LiaMn2GbO4 (0.90≤a≤1.8 and 0.001 ≤b≤0.1); LiaMn1-gGgPO4 (0.90≤a≤1.8 and 0≤g≤0.5);
Li(3-f)Fe2(PO4)3 (0≤f≤2); or LiaFePO4 (0.90≤a≤1.8).
[0066] In the above Chemical Formulas, A is or includes at least one of Ni, Co, Mn, or a
combination thereof; X is or includes at least one of Al, Ni, Co, Mn, Cr, Fe, Mg,
Sr, V, a rare earth element or a combination thereof; D is or includes at least one
of O, F, S, P, or a combination thereof; G is or includes at least one of Al, Cr,
Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; and L1 is or includes at least
one of Mn, Al, or a combination thereof.
[0067] The positive electrode active material may be or include, for example, a high nickel-based
positive electrode active material having a nickel content that is greater than or
equal to about 80 mol%, greater than or equal to about 85 mol%, greater than or equal
to about 90 mol%, greater than or equal to about 91 mol%, or greater than or equal
to about 94 mol% and less than or equal to about 99 mol% based on 100 mol% of the
metal excluding lithium in the lithium transition metal composite oxide. The high-nickel-based
positive electrode active material may be configured to achieve high capacity, and
can be applied to a high-capacity, high-density rechargeable lithium battery.
[0068] The negative electrode active material may include at least one of a material that
reversibly intercalates/deintercalates lithium ions, a lithium metal, a lithium metal
alloy, a material capable of doping/dedoping lithium, or a transition metal oxide.
[0069] The material that reversibly intercalates/deintercalates lithium ions may include
a carbon-based negative electrode active material, such as, for example, at least
one of crystalline carbon, amorphous carbon or a combination thereof. The crystalline
carbon may be or include graphite such as non-shaped, sheet-shaped, flake-shaped,
sphere-shaped, or fiber-shaped natural graphite or artificial graphite. The amorphous
carbon may be or include at least one of a soft carbon, a hard carbon, a mesophase
pitch carbonization product, calcined coke, and the like.
[0070] The lithium metal alloy includes an alloy of lithium and a metal such as or including
at least one of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge,
Al, and Sn.
[0071] The material capable of doping/dedoping lithium may be or include a Si-based negative
electrode active material or a Sn-based negative electrode active material. The Si-based
negative electrode active material may include at least one of silicon, a silicon-carbon
composite, SiOx (0 < x < 2), a Si-Q alloy (where Q is or includes at least one of
an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element (excluding
Si), a Group 15 element, a Group 16 element, a transition metal, a rare earth element,
and a combination thereof). The Sn-based negative electrode active material may include
at least one of Sn, SnO2, a Sn-based alloy, or a combination thereof.
[0072] The silicon-carbon composite may be or include a composite of silicon and amorphous
carbon. According to an example embodiment, the silicon-carbon composite may be in
a form of silicon particles, and amorphous carbon coated on the surface of the silicon
particles. For example, the silicon-carbon composite may include a secondary particle
(core) in which primary silicon particles are assembled, and an amorphous carbon coating
layer (shell) on the surface of the secondary particle. The amorphous carbon may also
be between the primary silicon particles, and, for example, the primary silicon particles
may be coated with the amorphous carbon. The secondary particle may be dispersed in
an amorphous carbon matrix.
[0073] The silicon-carbon composite may further include crystalline carbon. For example,
the silicon-carbon composite may include a core including crystalline carbon and silicon
particles, and an amorphous carbon coating layer on a surface of the core.
[0074] The Si-based negative electrode active material or the Sn-based negative electrode
active material may be included in combination with a carbon-based negative electrode
active material.
[0075] The conductive material may be included to impart conductivity (e.g., electrical
conductivity) to the electrode. Any material that does not cause chemical change (e.g.,
does not cause an undesirable chemical change in the rechargeable lithium battery),
and that conducts electrons, can be included in the battery. Examples of the conductive
material may include a carbon-based material such as at least one of natural graphite,
artificial graphite, carbon black, acetylene black, ketjen black, a carbon fiber,
a carbon nanofiber, and carbon nanotube; a metal-based material containing at least
one of copper, nickel, aluminum, silver, and the like, in a form of a metal powder
or a metal fiber; a conductive polymer such as a polyphenylene derivative; or a mixture
thereof.
[0076] As illustrated in FIG. 2, the dry electrode film may be manufactured through a dry
process. In the specification, the dry process or the dry electrode may refer to a
process or an electrode which includes no or substantially no solvent, or in which
a solvent is not intentionally included in an electrode manufacturing process. The
solvent may include a process solvent, a process solvent residue, process solvent
impurities, and the like. The dry electrode film may include a dry active material
and a dry binder, and may be formed in a sheet form. The dry binder may be or include
a binder which is not impregnated with the solvent. The dry binder may be or include
a binder which includes no solvent.
[0077] The dry binder may include a fibrillized binder. The fibrillized binder may be configured
as a matrix which supports and binds the dry active material and/or other components
included in the dry electrode film. The fibrillized binder may be confirmed in a fibrous
form in a scanning electron microscope image for the dry electrode film. The fibrillized
binder may have an aspect ratio in a range of about 10 or more, 20 or more, 50 or
more, or 100 or more.
[0078] In some example embodiments, the dry binder may include at least one of polytetrafluoroethylene
(PTFE), a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene
fluoride (PVDF), polyvinyl alcohol, polyacrylonitrile (PAN), carboxymethyl cellulose
(CMC), starch, hydroxypropyl cellulose, cellulose, polyvinyl pyrrolidone, polyethylene,
polypropylene, an ethylene-propylene-diene monomer (EPDM), a sulfonated-EPDM, styrene
butadiene rubber (SBR), fluoroelastomer, or copolymers thereof. However, the dry binder
is not limited thereto, and may include any binder for manufacturing the dry electrode
film. For example, the dry binder may include a fluorine-based binder. The fluorine-based
binder may include at least one of polytetrafluoroethylene (PTFE), a polyvinylidene
fluoride-hexafluoropropylene (PVDF-HFP) copolymer, or polyvinylidene fluoride (PVDF).
The content of the dry binder may be in a range of about 0.5 wt% to about 10 wt%,
or 1 wt% to 5 wt% for the total weight of the dry electrode film. The dry electrode
film may include the dry binder in the above-described range, and thus the cohesion
force between the dry electrode film and the substrate may be improved, and the dry
electrode including the dry electrode film may maintain the high energy density.
[0079] According to some example embodiments, the dry electrode film may include the electrode
powder including the active material, the conductive material, and the binder. The
dry electrode film may have a sheet shape, which is manufactured by calendaring the
electrode powder and has a given thickness, and have the yield strength of about 2.3
MPa or more in a sheet shape state. Porosity of the dry electrode film may be in a
range of about 50 % to about 70 %. The angle of internal friction (AIF) of the electrode
powder may be in a range of about 30° to about 50°. For example, the tensile strength
of the dry electrode film may be in a range of about 0.5 MPa or more.
[0080] According to some example embodiments, the electrode active material may include
at least one of nickel cobalt aluminum (NCA), lithium ferrophosphate (LFP), and graphite.
However, the present disclosure is not limited thereto.
[0081] The dry electrode may include the dry electrode film and the substrate. The dry electrode
film may be disposed on at least one surface of the substrate.
[0082] The substrate may include a material which may not cause chemical changes, and that
has high conductivity. For example, the substrate may include at least one of copper,
aluminum, stainless use steel (SUS), nickel, a polymer coated with a conductive material,
titanium, fired carbon, or a combination thereof.
[0083] In some example embodiments, the substrate may be formed in a metal foil or a thin
metal plate form such as at least one of copper, a copper alloy, nickel, or a nickel
alloy. In other example embodiments, the substrate may be formed in a metal foil or
a thin metal plate form such as aluminum or an aluminum alloy.
[0084] The flowcharts of FIG. 1 and FIG. 2 and the detailed descriptions therefor are merely
examples of the present disclosure, and the scope of the present disclosure is not
limited to the flowcharts of FIG. 1 and FIG. 2 and the detailed descriptions therefor.
For example, one or more processes in the flowcharts and the detailed descriptions
therefor may be added/changed/deleted, the order of one or more processes may be changed,
and one or more processes may be performed simultaneously.
[0085] FIG. 3 is a diagram illustrating an example of a mold and a pressurizing member according
to some example embodiments of the present disclosure. FIG.4 is a diagram illustrating
an example of filling an electrode powder in a mold according to some example embodiments
of the present disclosure. FIG. 5 is a diagram illustrating an example of an electrode
powder filled in a mold and a pressurizing member according to some example embodiments
of the present disclosure. FIG. 6 is a diagram illustrating an example of pressurizing
an electrode powder filled in a mold according to some example embodiments of the
present disclosure. FIG. 7 is a diagram illustrating an example of a specimen manufactured
using an electrode powder according to some example embodiments of the present disclosure.
[0086] Referring to FIG. 3 to FIG. 7, the specimen 800 may be manufactured using the electrode
powder 520 through the mold 510. The mold 510 may include a cylindrical cavity formed
in an inside thereof. The pressurizing member 530 may include a protrusion part to
be inserted into the cavity of the mold 510. However, the shapes of the mold 510 and
the pressurizing member 530 are not limited thereto, and may have various shapes.
[0087] A material for the mold 510 may be determined according to processability, process
conditions, and the like. For example, the material for the mold 510 may include at
least one of steel, aluminum (Al), a copper alloy, ceramic, carbon fiber, and the
like.
[0088] The electrode powder 520 may include the active material, the conductive material,
and the binder. The active material may include the positive electrode active material
and the negative electrode active material. The positive electrode active material
may include at least one of nickel cobalt aluminum (NCA), lithium ferrophosphate (LFP),
and the like, and the negative electrode active material may include graphite. However,
the present disclosure is not limited thereto.
[0089] According to some example embodiments, the electrode powder 520 may be filled in
the cavity of the mold 510. For example, the electrode powder 520 may be filled in
the mold 510 so that the weight of the electrode powder 520 filled within the mold
510 is in a range of about 1 g to about 5 g. Accordingly, the specimen 800 may be
readily manufactured with a small amount of electrode powder 520, and the yield strength
of the specimen 800 may be measured. However, the weight of the filled electrode powder
520 is not limited thereto.
[0090] According to some example embodiments, the electrode powder 520 may be pressurized
at a pressure in a range of about 10 MPa to about 100 MPa by the pressurizing member
530. Accordingly, the specimen 800 may be manufactured by pressurizing the electrode
powder 520 at various pressures, and thus the specimens 800 corresponding to dry electrode
films to be manufactured under various pressure conditions may be manufactured. For
example, when the dry electrode films have various densities according to various
process conditions, the electrode powder 520 may be pressurized at various pressures,
and thus the specimen 800 corresponding to the density of the dry electrode film may
be manufactured. Accordingly, before the dry electrode film is manufactured, the mechanical
property of the specimen 800 may be measured, and the mechanical property of the dry
electrode film may be measured in advance. However, the pressure applied to the electrode
powder 520 is not limited thereto, and the electrode powder 520 may be pressurized
at a wide range of pressure.
[0091] FIG. 8 is a diagram illustrating an example of a specimen pressurized by a jig and
measure equipment which measures a load according to some example embodiment of the
present disclosure, and FIG. 9 is a diagram illustrating Equation 1 discussed below
for calculating a yield strength of a specimen based on a measured load according
to some example embodiment of the present disclosure.
[0092] Referring to FIG. 8, the specimen 800 may be pressurized to be destroyed using a
jig 900. The jig 900 may have various shapes and sizes which may apply the pressure
to the specimen 800. The jig 900 may be coupled to measurement equipment 910 which
may measure a load. The measurement equipment 910 may measure the load applied at
a specific moment.
[0093] The specimen 800 may be pressurized to be destroyed using the jig 900. For example,
the specimen 800 may be pressurized by the jig 900 in an unconfined state. Then, the
load applied to the specimen 800 at a moment when the specimen 800 is destroyed may
be measured. As illustrated in FIG. 9, the load applied to the specimen 800 at the
moment when the specimen 800 is destroyed may be a load corresponding to a maximum
value in the graph.
[0094] The yield strength of the specimen 800 may be calculated based on the measured load.
For example, the yield strength of the specimen 800 may be a yield strength of the
specimen 800 calculated based on Equation 1 discussed below, for example, an unconfined
yield strength (UYS). The unconfined yield strength (UYS) may refer to a maximum compressive
strength of the electrode powder 520 in a state where a side of the specimen 800 is
unconfined when the specimen 800 is simply pressurized without confinement of the
side.

[0095] In the equation illustrated in FIG. 9, "c" may correspond to a value of 0.001 as
a unit conversion constant, "m" may correspond to a measured load (kg), "g" may correspond
to an acceleration of gravity (m/s
2), and "A" may correspond to a cross-sectional area (m
2) of the specimen. Accordingly, the equation illustrated in FIG. 9 may correspond
to the above-described Equation 1.
[0096] After the process of calculating the yield strength of the specimen 800, the method
S300 for manufacturing a dry electrode film illustrated in FIG. 1 may further include
a process of crushing the electrode powder when the yield strength calculated by Equation
1 is less than a given value. Through the crushing process, the binder may be crushed
in a fine fiber form, and thus a surface area of the binder may be increased, the
particles may be finer, and the porosity may be increased. Accordingly, the mechanical
property of the dry electrode film may be improved.
[0097] When the dry electrode is manufactured using the dry electrode film, it may be desirable
that the tensile strength of the dry electrode film is in a range of about 0.5 MPa
or more so as to facilitate manufacturing and handling. According to the following
Equation 2, when the yield strength of the dry electrode film is in a range of about
2.3 MPa or more, the tensile strength of the dry electrode film may be in a range
of about 0.5 MPa or more in the angle of internal friction (AIF) of the electrode
powder (see 520 of FIG. 4) of about 40°. Accordingly, it may be desirable that the
yield strength of the specimen 800 is in a range of about 2.3 MPa or more.
[0098] When the test result of the yield strength satisfies a predetermined or desired criterion,
the dry electrode film may be manufactured. Accordingly, when the yield strength of
the specimen 800 is in a range of about 2.3 MPa or more, the sheet type dry electrode
film having a given thickness may be manufactured through the calendaring process.
[0099] After the yield strength of the specimen 800 is calculated, when the yield strength
calculated by Equation 1 is less than about 2.3 MPa, the electrode powder 520 may
be additionally crushed. When the additionally crushed electrode powder 520 satisfies
the above-described test result of the yield strength, the dry electrode film may
be manufactured.
[0100] FIG. 10 is a diagram illustrating Equation 2 discussed below for calculating a tensile
strength of a specimen based on a measured angle of internal friction (AIF) and a
calculated yield strength of a specimen according to some example embodiments of the
present disclosure.
[0101] After the process of calculating the yield strength of the specimen (see 800 of FIG.
7), the angle of internal friction (AIF) of the electrode powder (see 520 of FIG.
2) may be measured, and the tensile strength of the specimen 800 may be calculated.
The tensile strength may refer to tolerable maximum stress when the specimen 800 receives
a tensile load.
[0102] The angle of internal friction (AIF) of the electrode powder 520 may be a property
indicating a resistance which is generated when particles in the electrode powder
520 slide against each other. The angle of internal friction (AIF) of the electrode
powder 520 may be measured by a powder fluidity evaluation method. The powder fluidity
evaluation method may be a method which may calculate the angle of internal friction
(AIF) by measuring the resistance which appears when the electrode powder receives
shear force.
[0103] The tensile strength of the specimen 800 may be calculated based on the calculated
unconfined yield strength (UYS) of the specimen 800 and the measured angle of internal
friction (AIF) of the electrode powder 520. For example, the tensile strength of the
specimen 800 may be calculated based on Equation 2 below.

[0104] In the equation illustrated in FIG. 10, "σ
t" may be the tensile strength (kPa), "φ" may be the angle of internal friction (°
), and "σ
u" may be the yield strength (kPa). Accordingly, the equation illustrated in FIG. 10
may correspond to the above-described Equation 2.
[0105] When manufacturing the dry electrode using the dry electrode film, it may be desirable
that the tensile strength of the dry electrode film is in a range of about 0.5 MPa
or more so as to facilitate manufacturing and handing. Accordingly, it may be desirable
that the tensile strength of the specimen 800 is in a range of about 0.5 MPa or more.
[0106] When the test result of the tensile strength satisfies a predetermined or desired
criterion, the dry electrode film may be manufactured. Accordingly, when the tensile
strength of the specimen 800 is in a range of about 0.5 MPa or more, the sheet type
dry electrode film having a given thickness may be manufactured through a calendaring
process.
[0107] After the tensile strength of the specimen 800 is calculated, when the tensile strength
calculated by Equation 2 is less than about 0.5 MPa, the electrode powder 520 may
be additionally crushed. When the additionally crushed electrode powder 520 satisfies
the above-described test result of the tensile strength, the dry electrode film may
be manufactured.
[0108] FIG. 11 illustrates a cross-sectional view of an example of a dry electrode according
to some example embodiments of the present disclosure.
[0109] Referring to FIG. 11, a dry electrode may include a dry electrode film 110 and a
substrate 120. The dry electrode film 110 may be disposed on at least one surface
of the substrate 120.
[0110] The dry electrode film 110 may include an active material, a conductive material,
and a binder. For example, the active material may be a positive electrode active
material or a negative electrode active material.
[0111] The positive electrode active material may include a compound (lithiated intercalation
compound) that is capable of intercalating and deintercalating lithium. For example,
at least one of a composite oxide of lithium and a metal such as or including at least
one of cobalt, manganese, nickel, and combinations thereof may be included.
[0112] The composite oxide may be or include a lithium transition metal composite oxide.
Specific examples of the composite oxide may include at least one of lithium nickel-based
oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based
compound, cobalt-free nickel-manganese-based oxide, or a combination thereof.
[0113] As an example, the following compounds represented by any one of the following Chemical
Formulas may be included. Li
aA
1-bX
bO
2-cD
c (0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); Li
aMn
2-bX
bO
4-cD
c (0.90≤a≤1.8, 0≤b≤0.5, and 0≤c≤0.05); Li
aNi
1-b-cCo
bX
cO
2-αD
α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, and 0< α <2); Li
aNi
1-b-cMn
bX
cO
2-αD
α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, and 0< α <2); Li
aNi
bCo
cL
1dGeO
2 (0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, and 0≤e≤0.1); Li
aNiG
bO
2 (0.90≤a≤1.8 and 0.001≤b≤0.1); Li
aCoG
bO
2 (0.90≤a≤1.8 and 0.001 ≤b≤0.1); Li
aMn
1-bG
bO
2 (0.90≤a≤1.8 and 0.001≤b≤0.1); Li
aMn
2G
bO
4 (0.90≤a≤1.8 and 0.001 ≤b≤0.1); Li
aMn
1-gG
gPO
4 (0.90≤a≤1.8 and 0≤g≤0.5); Li
(3-f)Fe
2(PO
4)
3 (0≤f≤2); or Li
aFePO
4 (0.90≤a≤1.8).
[0114] In the above Chemical Formulas, A is or includes at least one of Ni, Co, Mn, or a
combination thereof; X is or includes at least one of Al, Ni, Co, Mn, Cr, Fe, Mg,
Sr, V, a rare earth element or a combination thereof; D is or includes at least one
of O, F, S, P, or a combination thereof; G is or includes at least one of Al, Cr,
Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; and L1 is or includes at least
one of Mn, Al, or a combination thereof.
[0115] The positive electrode active material may be or include, for example, a high nickel-based
positive electrode active material having a nickel content that is greater than or
equal to about 80 mol%, greater than or equal to about 85 mol%, greater than or equal
to about 90 mol%, greater than or equal to about 91 mol%, or greater than or equal
to about 94 mol% and less than or equal to about 99 mol% based on 100 mol% of the
metal excluding lithium in the lithium transition metal composite oxide. The high-nickel-based
positive electrode active material may be configured to achieve high capacity, and
can be applied to a high-capacity, high-density rechargeable lithium battery.
[0116] The negative electrode active material may include at least one of a material that
reversibly intercalates/deintercalates lithium ions, a lithium metal, a lithium metal
alloy, a material capable of doping/dedoping lithium, or a transition metal oxide.
[0117] The material that reversibly intercalates/deintercalates lithium ions may include
a carbon-based negative electrode active material, such as, for example, at least
one of crystalline carbon, amorphous carbon or a combination thereof. The crystalline
carbon may be or include graphite such as non-shaped, sheet-shaped, flake-shaped,
sphere-shaped, or fiber-shaped natural graphite or artificial graphite. The amorphous
carbon may be or include at least one of a soft carbon, a hard carbon, a mesophase
pitch carbonization product, calcined coke, and the like.
[0118] The lithium metal alloy includes an alloy of lithium and a metal such as or including
at least one of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge,
Al, and Sn.
[0119] The material capable of doping/dedoping lithium may be or include a Si-based negative
electrode active material or a Sn-based negative electrode active material. The Si-based
negative electrode active material may include at least one of silicon, a silicon-carbon
composite, SiOx (0 < x < 2), a Si-Q alloy (where Q is or includes at least one of
an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element (excluding
Si), a Group 15 element, a Group 16 element, a transition metal, a rare earth element,
and a combination thereof). The Sn-based negative electrode active material may include
at least one of Sn, SnO2, a Sn-based alloy, or a combination thereof.
[0120] The silicon-carbon composite may be or include a composite of silicon and amorphous
carbon. According to an example embodiment, the silicon-carbon composite may be in
a form of silicon particles, and amorphous carbon coated on the surface of the silicon
particles. For example, the silicon-carbon composite may include a secondary particle
(core) in which primary silicon particles are assembled, and an amorphous carbon coating
layer (shell) on the surface of the secondary particle. The amorphous carbon may also
be between the primary silicon particles, and, for example, the primary silicon particles
may be coated with the amorphous carbon. The secondary particle may be dispersed in
an amorphous carbon matrix.
[0121] The silicon-carbon composite may further include crystalline carbon. For example,
the silicon-carbon composite may include a core including crystalline carbon and silicon
particles, and an amorphous carbon coating layer on a surface of the core.
[0122] The Si-based negative electrode active material or the Sn-based negative electrode
active material may be included in combination with a carbon-based negative electrode
active material.
[0123] The conductive material may be included to impart conductivity to the electrode.
Any material that does not cause chemical change and conducts electrons can be included
in the battery. Examples of the conductive material may include a carbon-based material
such as at least one of natural graphite, artificial graphite, carbon black, acetylene
black, ketjen black, a carbon fiber, a carbon nanofiber, and carbon nanotube; a metal-based
material containing at least one of copper, nickel, aluminum, silver, and the like,
in a form of a metal powder or a metal fiber; a conductive polymer such as a polyphenylene
derivative; or a mixture thereof.
[0124] The dry electrode film 110 may be manufactured through a dry process, for example,
a dry process as explained above with reference to FIG. 1 to FIG. 10. In the specification,
the dry process or the dry electrode may refer to a process or an electrode which
includes no solvent, or in which a solvent is not intentionally included in an electrode
manufacturing process. The solvent may include a process solvent, a process solvent
residue, process solvent impurities, and the like. The dry electrode film 110 may
include a dry active material and a dry binder, and may be formed in a sheet form.
The dry binder may be or include a binder which is not impregnated with the solvent.
The dry binder may be or include a binder which includes no solvent.
[0125] The dry binder may include a fibrillized binder. The fibrillized binder may be configured
as a matrix which supports and binds the dry active material and/or other components
included in the dry electrode film 110. The fibrillized binder may be confirmed in
a fibrous form in a scanning electron microscope image for the dry electrode film
110. The fibrillized binder may have an aspect ratio in a range of about 10 or more,
20 or more, 50 or more, or 100 or more.
[0126] In some example embodiments, the dry binder may include at least one of polytetrafluoroethylene
(PTFE), a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene
fluoride (PVDF), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC),
starch, hydroxypropyl cellulose, cellulose, polyvinyl pyrrolidone, polyethylene, polypropylene,
an ethylene-propylene-diene monomer (EPDM), a sulfonated-EPDM, styrene butadiene rubber
(SBR), fluoroelastomer, or copolymers thereof. However, the dry binder is not limited
thereto, and may include any binder for manufacturing the dry electrode film. The
dry binder may include a fluorine-based binder. The fluorine-based binder may include
at least one of polytetrafluoroethylene (PTFE), a polyvinylidene fluoride-hexafluoropropylene
(PVDF-HFP) copolymer, or polyvinylidene fluoride (PVDF). The content of the dry binder
may be in a range of about 0.5 wt% to about 10 wt%, or 1 wt% to 5 wt% for the total
weight of the dry electrode film 110. The dry electrode film 110 may include the dry
binder in the above-described range, and thus the cohesion force between the dry electrode
film 110 and the substrate 120 may be improved, and the dry electrode 100 including
the dry electrode film 110 may maintain the high energy density.
[0127] According to some example embodiments, the dry electrode film 110 may include the
electrode powder including the active material, the conductive material, and the binder.
The dry electrode film 110 may have a sheet shape, which is manufactured by calendaring
the electrode powder and has a given thickness, and have the yield strength of about
2.3 MPa or more in a sheet shape state. Porosity of the dry electrode film 110 may
be in a range of about 50 % to about 70 %. The angle of internal friction of the electrode
powder may be in a range of about 30° to about 50°. For example, the tensile strength
of the dry electrode film may be in a range of about 0.5 MPa or more.
[0128] According to some example embodiments, the electrode active material may include
at least one of nickel cobalt aluminum (NCA), lithium ferrophosphate (LFP), and graphite.
However, the present disclosure is not limited thereto.
[0129] The substrate 120 may include a material which may not cause chemical changes, and
that has high conductivity. For example, the substrate 120 may include at least one
of copper, aluminum, stainless steel, nickel, a polymer coated with a conductive material,
titanium, fired carbon, or a combination thereof.
[0130] In some example embodiments, the substrate 120 may be formed in a metal foil or a
thin metal plate form such as at least one of copper, a copper alloy, nickel, or a
nickel alloy. In other example embodiments, the substrate 120 may be formed in a metal
foil or a thin metal plate form such as aluminum or an aluminum alloy.
[0131] Although the present disclosure has been described above with respect to example
embodiments thereof, the present disclosure is not limited thereto. Various modifications
and variations can be made thereto by those skilled in the art within the spirit of
the present disclosure and the equivalent scope of the appended claims.
DESCRIPTION OF SOME REFERENCE SYMBOLS:
[0132]
510: mold
520: electrode powder
530: pressurizing member
800: specimen
900: jig
910: measuring equipment